U.S. patent application number 14/517690 was filed with the patent office on 2015-05-14 for use of styrene butadiene block co polymers having reduced styrene content in the preparation of polymer modified asphalt binder.
This patent application is currently assigned to Innophos, Inc.. The applicant listed for this patent is Innophos, Inc.. Invention is credited to JEAN VALERY MARTIN.
Application Number | 20150133586 14/517690 |
Document ID | / |
Family ID | 52828770 |
Filed Date | 2015-05-14 |
United States Patent
Application |
20150133586 |
Kind Code |
A1 |
MARTIN; JEAN VALERY |
May 14, 2015 |
USE OF STYRENE BUTADIENE BLOCK CO POLYMERS HAVING REDUCED STYRENE
CONTENT IN THE PREPARATION OF POLYMER MODIFIED ASPHALT BINDER
Abstract
Compositions and method for an asphalt and polymer composition
including a Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30%.
Inventors: |
MARTIN; JEAN VALERY;
(PRINCETON, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Innophos, Inc. |
Cranbury |
NJ |
US |
|
|
Assignee: |
Innophos, Inc.
Cranbury
NJ
|
Family ID: |
52828770 |
Appl. No.: |
14/517690 |
Filed: |
October 17, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61892098 |
Oct 17, 2013 |
|
|
|
Current U.S.
Class: |
524/71 |
Current CPC
Class: |
C08L 53/00 20130101;
C08L 95/00 20130101; C08L 95/00 20130101; C08L 53/02 20130101; C08L
2555/22 20130101 |
Class at
Publication: |
524/71 |
International
Class: |
C08L 95/00 20060101
C08L095/00; C08L 53/00 20060101 C08L053/00 |
Claims
1. A method for preparing an asphalt and polymer composition
comprising a Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% comprising the
steps of: a. heating a source of neat asphalt; b. adding an acid to
said neat asphalt before or after the addition of a
Styrene-Butadiene block copolymer wherein the styrene content of
said block copolymer does not exceed 30%; c. mixing to form said
asphalt and polymer composition; wherein further, said
Styrene-Butadiene block copolymer comprises from about 1 to about
20 wt. % of said asphalt and polymer composition, and wherein the
acid comprises from about 0.05 to about 2 wt. % of a total mixture
of said asphalt and polymer composition.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. 119(e) to
U.S. Provisional Application No. 61/892,098 filed Oct. 17, 2013,
incorporated herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for preparing an
asphalt and polymer composition comprising a Styrene-Butadiene
block copolymer wherein the styrene content of said block copolymer
does not exceed 30%.
BACKGROUND OF THE INVENTION
[0003] It has long been recognized that the properties of
conventional bitumen compositions can be modified by the addition
of other substances, such as polymers. A wide variety of polymers
have been used as additives in bitumen compositions. For example,
copolymers derived from styrene and conjugated dienes, such as
butadiene or isoprene, are particularly useful, since these
copolymers have good solubility in bitumen compositions and the
resulting modified-bitumen compositions have good rheological
properties.
[0004] As noted, various polymers have been added to asphalts to
improve physical and mechanical performance properties.
Polymer-modified asphalts (PMAs) are routinely used in the road
construction/maintenance and roofing industries. Conventional
asphalts often do not retain sufficient elasticity in use and,
also, exhibit a plasticity range that is too narrow for use in many
modern applications such as road construction. It is known that the
characteristics of road asphalts and the like can be greatly
improved by incorporating into them an elastomeric-type polymer
which may be one such as butyl, polybutadiene, polyisoprene or
polyisobutene rubber, ethylene/vinyl acetate copolymer,
polyacrylate, polymethacrylate, polychloroprene, polynorbornene,
ethylene/propylene/diene (EPDM) terpolymer and advantageously a
random or block copolymer of styrene and a conjugated diene. The
modified asphalts thus obtained commonly are referred to variously
as bitumen/polymer binders or asphalt/polymer mixes. Modified
asphalts and asphalt emulsions typically are produced utilizing
styrene/butadiene based polymers, and typically have raised
softening point, increased viscoelasticity, enhanced force under
strain, enhanced strain recovery, and improved low temperature
strain characteristics as compared with non-modified asphalts and
asphalt emulsions.
[0005] Presently, Applicants have discovered that the optimum
formulation of a PMA made with Styrene Butadiene or Styrene
Butadiene Rubber is achieved by carefully selecting a Styrene
Butadiene or Styrene Butadiene Rubber containing 30% by weight or
less of styrene.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a method for preparing an
asphalt and polymer composition comprising a Styrene-Butadiene
block copolymer wherein the styrene content of said block copolymer
does not exceed 30% by weight comprising the steps of: [0007] a.
heating a source of neat asphalt; [0008] b. adding an acid to said
neat asphalt before or after the addition of a Styrene-Butadiene
block copolymer wherein the styrene content of said block copolymer
does not exceed 30% by weight; [0009] c. mixing to form said
asphalt and polymer composition; wherein further, said
Styrene-Butadiene block copolymer comprises from about 1 to about
20 wt. % of said asphalt and polymer composition, and wherein the
acid comprises from about 0.05 to about 2 wt. % of a total mixture
of said asphalt and polymer composition.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The present invention relates to a method for preparing an
asphalt and polymer composition comprising a Styrene-Butadiene
block copolymer wherein the styrene content of said block copolymer
does not exceed 30% by weight comprising the steps of: [0011] a.
heating a source of neat asphalt; [0012] b. adding an acid to said
neat asphalt before or after the addition of a Styrene-Butadiene
block copolymer wherein the styrene content of said block copolymer
does not exceed 30% by weight; [0013] c. mixing to form said
asphalt and polymer composition; wherein further, said
Styrene-Butadiene block copolymer comprises from about 1 to about
20 wt. % of said asphalt and polymer composition, and wherein the
acid comprises from about 0.05 to about 2 wt. % of a total mixture
of said asphalt and polymer composition.
[0014] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
THE PRACTICE OF THE PRESENT INVENTION
[0015] U.S. Pat. No. 8,198,350, U.S. Pat. No. 6,031,029, U.S. Pat.
No. 6,228,909, U.S. Pat. No. 5,618,862, U.S. Pat. No. 5,880,185,
U.S. Pat. No. 6,011,095, U.S. Pat. No. 7,495,045, U.S. Pat. No.
7,417,082, U.S. Pat. No. 8,211,960, U.S. Pat. No. 7,968,628, and
U.S. Pat. No. 7,446,139 all disclose stepwise methods for preparing
modified asphalt. The Styrene-Butadiene block copolymer wherein the
styrene content of said block copolymer does not exceed 30% by
weight can be added at any time during the modified asphalt
preparation process.
[0016] In an embodiment of the invention, a cross-linked,
polymer-modified asphalt is prepared by a method comprising the
steps of: heating an asphalt; adding a crosslinking agent to the
asphalt and mixing to form an asphalt-crosslinking agent mixture;
and adding a crosslinkable polymer and an acid to the
asphalt-crosslinking agent mixture; wherein following the addition
of the crosslinking agent to the asphalt and the mixing to form an
asphalt-crosslinking agent mixture, the acid is added and mixed
with the asphalt-crosslinking agent mixture before the
crosslinkable polymer is added and mixed with the
asphalt-crosslinking agent mixture, thus forming a cross-linked,
polymer-modified asphalt.
[0017] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0018] In an embodiment of the invention, a polymer modified
asphalt is prepared according to the following process:
[0019] providing a source of a neat asphalt;
[0020] heating said neat asphalt;
[0021] providing a source of a phosphoric acid;
[0022] adding said acid to said neat asphalt, after the step of
heating said neat asphalt;
[0023] mixing said neat asphalt for a period of time of from
approximately 1 hour to approximately 2 hours, after the step of
adding said acid;
[0024] further heating said neat asphalt to a temperature of from
approximately 300.degree. F. to approximately 400.degree. F., after
the step of mixing said neat asphalt;
[0025] providing a source of a polymer;
[0026] adding said polymer to said neat asphalt to form a blend,
after the step of further heating said neat asphalt;
[0027] providing a source of a dilution asphalt;
[0028] adding said blend to said dilution asphalt to form a diluted
product; and
[0029] mixing said diluted product.
[0030] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0031] In an embodiment of the invention, a composition suitable
for use as a polymer modified asphalt is made by a plurality of
steps, said plurality of steps comprising:
[0032] providing a source of a neat asphalt;
[0033] heating said neat asphalt;
[0034] providing a source of a phosphoric acid;
[0035] adding said acid to said neat asphalt, after the step of
heating said neat asphalt;
[0036] mixing said neat asphalt for a period of time of from
approximately 1 hour to approximately 2 hours, after the step of
adding said acid;
[0037] further heating said neat asphalt to a temperature of from
approximately 300.degree. F. to approximately 400.degree. F., after
the step of mixing said neat asphalt;
[0038] providing a source of a polymer;
[0039] adding said polymer to said neat asphalt to form a blend,
after the step of further heating said neat asphalt;
[0040] providing a source of a dilution asphalt;
[0041] adding said blend to said dilution asphalt to form a diluted
product; and mixing said diluted product.
[0042] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0043] Another embodiment of the invention relates to a process for
the preparation of bitumen/polymer compositions with a reinforced
multigrade character, in which, while operating at temperatures of
between 100.degree. C. and 230.degree. C. and with agitation for a
period of at least 10 minutes, a bitumen or mixture of bitumens is
brought into contact with, calculated by weight of bitumen or
mixture of bitumens, 0.5% to 20% of a sulphur-crosslinkable
elastomer and a sulphur-donating coupling agent in a quantity such
as to provide a quantity of free sulphur representing 0.1% to 20%
of the weight of the sulphur-crosslinkable elastomer in the
reaction mixture formed from the bitumen or mixture of bitumens,
elastomer and coupling agent ingredients, in order to produce a
sulphur-crosslinked composition, wherein in the said process the
reaction mixture resulting from the sulphur vulcanization, is
maintained at a temperature of between 100.degree. C. and
230.degree. C. and with agitation, there is incorporated 0.005% to
5%, by weight of the bitumen or mixture of bitumens, of an
inorganic adjuvant consisting of at least one compound selected
from the group consisting of phosphoric acids, boric acids,
sulphuric acid, the anhydrides of the said acids and
chlorosulphuric acid, and the reaction mixture containing the
inorganic adjuvant is maintained at the temperature of between
100.degree. C. and 230.degree. C. and with agitation for a period
of at least 20 minutes.
[0044] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0045] Another embodiment of the invention relates to a process for
the preparation of bitumen/polymer compositions with a reinforced
multigrade nature, in which a bitumen or a mixture of bitumens is
brought into contact, the operation being carried out at
temperatures of between 100.degree. C. and 230.degree. C. and with
stirring for a period of time of at least 10 minutes, with, with
respect to the weight of the bitumen or mixture of bitumens, 0.5%
to 20% of a sulphur-crosslinkable elastomer and a sulphur-donor
coupling agent in an amount capable of providing an amount of free
sulphur representing 0.1% to 20% of the weight of the
sulphur-crosslinkable elastomer in the reaction mixture formed from
the ingredients bitumen or mixture of bitumens, elastomer and
coupling agent, in order to produce a sulphur-crosslinked
composition, 0.005% to 5%, by weight of the bitumen or mixture of
bitumens, of an acidic adjuvant being then incorporated in the
reaction mixture resulting from the crosslinking with sulphur which
is maintained at a temperature of between 100.degree. C. and
230.degree. C., accompanied by stirring and the reaction mixture
containing the acidic adjuvant is maintained at a temperature of
between 100.degree. C. and 230.degree. C., with stirring, for a
period of time of at least 10 minutes, and wherein, in the said
process, the acidic adjuvant is selected from the group consisting
of polyphosphoric acids, acids of the formula
R--(COO).sub.t--SO.sub.3 H, where t is 0 or 1 and R is a monovalent
C.sub.1 to C.sub.12 hydrocarbyl radical, mixtures of at least one
polyphosphoric acid and sulphuric acid, mixtures of at least one
polyphosphoric acid and of at least one of the said acids
R--(COO).sub.t--SO.sub.3 H, mixtures of sulphuric acid and of at
least one of the acids R--(COO).sub.t--SO.sub.3 H, and mixtures of
sulphuric acid with at least one polyphosphoric acid and at least
one of the acids R--(COO).sub.t--SO.sub.3 H.
[0046] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0047] A further embodiment of the invention relates to a process
for the preparation of bitumen/polymer compositions in which a
bitumen or mixture of bitumens is brought into contact, the
operation being carried out at temperatures between 100.degree. C.
and 230.degree. C. and with stirring for a time of at least 10
minutes, with, with respect to the weight of the bitumen or mixture
of bitumens, 0.01% to 20% of at least one olefinic polymer carrying
epoxy or COOH functional groups, in order to form a so-called
bitumen/polymer component reaction product, the said process
comprising maintaining the bitumen/polymer component at
temperatures of between 100.degree. C. and 230.degree. C. and with
stirring, incorporating 0.005% to 6%, by weight of the bitumen or
mixture of bitumens, of an acidic adjuvant and the reaction mixture
thus formed is maintained at temperatures of between 100.degree. C.
and 230.degree. C. and with stirring for a time of at least 10
minutes in order to produce the bitumen/polymer composition, the
said acidic adjuvant being composed of one or more compounds
selected from the group consisting of phosphoric acids, boric
acids, sulphuric acid, the anhydrides of the said acids,
chlorosulphuric acid, polyphosphoric acids, phosphonic acids of
formula ##STR19## and acids of formula R--(COO).sub.t--SO.sub.3 H
with, in the said formulae, t taking the value of zero or one and R
denoting a monovalent hydrocarbon radical selected from the group
consisting of C.sub.1 to C.sub.6 acyclic monovalent hydrocarbon
radicals and cyclic monovalent hydrocarbon radicals containing 4 to
12 cyclic carbon atoms and optionally substituted by C.sub.1 to
C.sub.16 acyclic monovalent hydrocarbon radicals. The
Styrene-Butadiene block copolymer wherein the styrene content of
said block copolymer does not exceed 30% by weight can be added at
any time during the modified asphalt preparation process.
[0048] An embodiment of the invention relates to a method for
preparing asphalt and polymer compositions comprising: heating an
asphalt; adding an elastomeric polymer comprised of a vinyl
aromatic/conjugated diene and mixing to form a mixture; adding
polyphosphoric acid to the asphalt before or after the polymer and
mixing to form another mixture; adding a crosslinker to the mixture
after the addition of the acid and mixing to form polymer modified
acid (PMA); and wherein the elastomeric polymer comprises from
about 1 to about 20 wt. % of the PMA, and wherein the acid
comprises from about 0.05 to about 2 wt. % of a total mixture of
the PMA. The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0049] An embodiment of the invention relates to a method for
making a modified asphalt binder composition, comprising the steps
of: a. providing neat asphalt in an appropriate vessel; b. heating
the neat asphalt to a temperature of between about 120.degree. C.
and about 200.degree. C.; c. adding to the neat asphalt a first
modifying ingredient selected from the group consisting of crumb
rubber, at least one acid, and one or more synthetic polymers; d.
mixing the asphalt and the first modifying ingredient with one of a
high shear mixer or a low shear mixer for a period of between about
5 minutes and about 10 hours; e. adding a second modifying
ingredient selected from the group consisting of crumb rubber, at
least one acid, one or more synthetic polymers, and a cross-linking
agent, wherein the second modifying ingredient is a different type
of modifying ingredient than the first modifying ingredient, and
the second modifying ingredient may be a cross-linking agent only
if the first modifying ingredient is crumb rubber; f. mixing the
second modifying ingredient and the asphalt with one of a high
shear mixer or a low shear mixer for a period of between about 5
minutes and about 10 hours g. adding a third modifying ingredient
selected from the group consisting of crumb rubber, at least one
acid one or more synthetic polymers and a cross-linking agent,
wherein the third modifying ingredient is a different type of
modifying ingredient than the first modifying ingredient and the
second modifying ingredient, and the third modifying ingredient may
be a cross-linking agent only if the first or the second modifying
ingredient is crumb rubber; h. agitating the third modifying
ingredient and the asphalt with one of a high shear mixer or a low
shear mixer for a period of between about 5 minutes and about 48
hours; i. adding a fourth modifying ingredient selected from the
group consisting of at least one acid one or more synthetic
polymers and a cross-linking agent, wherein the third modifying
ingredient is a different type of modifying ingredient than the
first modifying ingredient, the second modifying ingredient, and
the third modifying ingredient; and j. agitating the fourth
modifying ingredient and the asphalt with a low shear mixer for a
period of between about 5 minutes and about 48 hours.
[0050] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0051] A further embodiment of the invention relates to a method
for producing a crumb rubber modified asphalt comprising the steps
of: a) heating a pre-selected quantity of asphalt to a temperature
of between about 325.degree. F. to 550.degree. F.; b) adding crumb
rubber and a mineral acid to the heated asphalt with stirring; and
c) blowing air through the asphalt, crumb rubber and mineral acid
mixture.
[0052] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0053] An embodiment of the invention relates to a modified asphalt
binder composition, comprising: a. about 60% by weight to about
98.9% by weight asphalt binder material; b. about 0.1% by weight to
about 30% by weight crumb rubber; c. about 0.05% by weight to about
5% by weight of at least one acid selected from the group
consisting of phosphoric acid, polyphosphoric acid, sulfuric acid
at more than 90% wt, boric acid, adipic acid, citric acid, oxalic
acid, tartaric acid, maleic acid, valeric acid, succinic acid,
fumaric acid, glutamic acid, phtalic acid, acetic acid, and
combinations thereof; and d. about 0.01% by weight to about 5% by
weight of a cross-linking agent.
[0054] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0055] An embodiment of the invention relates to a method for
making a modified asphalt binder composition, comprising the steps
of: a. providing neat asphalt in an appropriate vessel; b. heating
the neat asphalt to a temperature of between about 120.degree. C.
and about 200.degree. C.; c. adding to the neat asphalt a first
modifying ingredient selected from the group consisting of at least
one acid, at least one synthetic polymer and crumb rubber; d.
mixing the asphalt and the first modifying ingredient with one of a
high shear mixer or a low shear mixer for a period of between about
5 minutes and about 10 hours e. adding to the modified asphalt
binder a second modifying ingredient selected from the group
consisting of at least one acid, at least one synthetic polymer and
crumb rubber, wherein the second modifying ingredient is a
different type of ingredient than the first modifying ingredient;
f. mixing the second modifying ingredient and the modified asphalt
binder in one of a high shear mixer or a low shear mixer for a
period of between about 5 minutes and about 10 hours g. adding to
the modified asphalt binder a third modifying ingredient selected
from the group consisting of at least one acid, at least one
synthetic polymer and crumb rubber, wherein the third modifying
ingredient is a different type of ingredient than the first
modifying ingredient and the second modifying ingredient; and h.
agitating the third modifying ingredient and the modified binder
material in one of a low shear mixer or a high shear mixer for a
period of between about 5 minutes and about 48 hours.
[0056] The Styrene-Butadiene block copolymer wherein the styrene
content of said block copolymer does not exceed 30% by weight can
be added at any time during the modified asphalt preparation
process.
[0057] Styrene-Butadiene block copolymers wherein the styrene
content of said block copolymer does not exceed 30% include, but
are not limited to, the following polymers:
TABLE-US-00001 Polymer Polystyrene content (% wt) Kraton D1192 28.5
to 32.5% Kraton D1116 21.2 to 24.2% INNOVALT XL200 Polyphosphoric
acid 105% wt equivalent
RESULTS
TABLE-US-00002 [0058] Softening Elastic Description Point (C.)
Recovery (%) Neat Bitumen 70/100 51 X Neat + 1.5% SBS D1192 + 0.2%
Crosslinker 65 63.7 X + 1% INNOVALT XL 200 Neat + 1.5% SBS D1192 +
0.2% Crosslinker 66 65.0 X + 1% INNOVALT XL 200 Neat + 2% SBS D1192
+ 0.2% Crosslinker 66 68.7 X + 0.5% INNOVALT XL 200 Neat + 2% SBS
D1116 + 0.2% Crosslinker 70 77.5 X + 0.5% INNOVALT XL 200
[0059] Suitable inorganic acids for use in the methods herein
include, but are not necessarily limited to, phosphoric acid,
polyphosphoric acid, sulfuric acid, hydrochloric acid, nitric acid,
and mixtures thereof. Herein, phosphoric acid includes
polyphosphoric acid. In one non-limiting embodiment, the proportion
of inorganic acid ranges from about 0.05 to about 2 wt % based on
the total mixture of asphalt, acid and polymer. In another
non-restrictive embodiment, the proportion of inorganic acid ranges
from about 0.05 to about 1 wt % based on the total mixture.
[0060] Various other additives suitable for the purposes herein
include, but are not necessarily limited to, known and future
accelerators, activators, divalent metal oxides (e.g. zinc oxide)
and the like. A variety of accelerators may be used in conjunction
herein, including, but not limited to, dithiocarbamates and
benzothiazoles. Many crosslinking agents and other additives are
normally sold in powder or flake form.
[0061] The methods and compositions described will be further
illustrated with respect to particular Examples that are only
intended to more fully illuminate the compositions and methods and
not limit them.
* * * * *